Alkenyl-substituted bisnadimides, process for manufacturing the same, process for curing the same, and adhesives and coating materials utilizing the same

ABSTRACT

An alkenyl-substituted bisnadimide represented by the following formula  1!: ##STR1##  wherein R 1  and R 2  individually represent a hydrogen atom or a methyl group, and E is an alkylene.phenylene group or an alkylene.phenylene.alkylene group represented by the following formula  2!: ##STR2##  (wherein a is an integer of 0 or 1, and R 3&#39;  individually represent a C 1  -C 4  alkylene group or a C 5  -C 8  cycloalkylene group)!, a process for the preparation of the same and a process for curing the same are disclosed. Further, an adhesive material and a coating material containing the bisnadimide as a curing component are also disclosed. A cured material obtaind from the bisnadimide has excellent heat resistance, mechanical strength, toughness, adhesion property to many kinds of substrates, and so on. The adhesive material shows excellent heat resistance and the coating material shows excellent boiling water resistance.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel alkenyl-substitutedbisnadimide, which is a thermosetting resin exhibiting excellentprocessability, heat resistance, mechanical strength, electricalcharacteristics, a process for manufacturing said alkenyl-substitutedbisnadimide, and a process for curing the same. Further, the presentinvention also relates to an adhesive and a coating material comprisingsaid novel alkenyl-substituted bisnadimide as a curing component. Thenovel alkenyl-substituted bisnadimide is useful as a laminatingmaterial, a cast molding material, a molding material, a coatingmaterial, a paint, an adhesive, a filler, and a matrix resin forcomposite resins in which glass or carbon fibers are used as areinforcing material. In particular, this alkenyl-substitutedbisnadimide exhibits superior heat resistance for a long period of timewhen used as an adhesive, and exhibits excellent resistance to boilingwater when used as a coating material.

2. Description of the Prior Art

There is an increasing demand for high performance and high functionalmaterials along with the advance of science and technology. A greatnumber of materials are being developed in order to satisfy this demand.Among these materials, applications of thermosetting resins haveexpanded to cover wide areas, including the areas of structuralmaterials for air crafts and the like, and the areas of electronic orelectrical materials, such as packaging materials for semiconductors,laminating materials, coating materials, and adhesives. A characteristicparticularly demanded of such thermosetting resins is excellent heatresistance. Further, various high performance polymers, which aregenerally called super engineering plastics, such as polyether ketones,polyphenylene sulfides, and polyimides, have been introduced to themarket. Among these, polyimides are materials of which the demand isexpected to expand in future.

Bisnadimide compounds possessing norbornene rings at the both ends andaromatic groups in the molecule have heretofore attracted a great dealof attention as a raw material for addition-type polyimide resins withextremely high heat resistance. Some of them have already been used as amatrix of forerunner composite materials. The bisnadimide compounds,however, have drawbacks in their high melting point, the insufficientsolubility in solvents, and the poor reactivity. These render thesecompounds difficult to handle and require severe reaction conditions topolymerize (e.g., 300° C. or higher molding temperature). The reactionsunder severe conditions not only promote polymerization reaction butalso partly accompany a reverse Diels-Alder reaction which producesvolatile cyclopentadiene. The cyclopentadiene vapor causes a greatnumber of boids to be produced in the molded products, impairingproperties thereof. Therefore, the application of bisnadimide isconsiderably limited. Molding of a bisnadimide resin is thereforelimited to a process using a high temperature under high pressure, suchas the autoclave molding process, or it can only be used as a vanishproduced by the oligomerization of raw materials of bisnadimide, i.e., anadic anhydride or an ester thereof and a diamine, dissolved in asolvent.

Various processes for introducing suitable substituent groups to thenorbornene ring of bisnadimide are investigated in order to eliminatethese drawbacks in bisnadimide.

One of the processes is introducing alkenyl groups such as allyl groupor methallyl group, and a number of proposals dealing with this processhave been reported, e.g., U.S. Pat. Nos. 4,515,962, 4,579,916,4,604,437, 4,666,997, 4,678,849, 4,709,047, 4,728,742, 4,777,236,4,778,898, 4,885,346, 4,966,923, 5,120,857, Japanese Patent Laid-openNo. Sho 63 (1988)-170358 and No. Sho 63 (1988)-310884, etc.

These proposals claim that the introduction of alkenyl groups, such asallyl group or methallyl group, lowers the melting point of thenadimide, increases its solubility in solvents, lowers curingtemperature to a certain degree, and prevents production of volatilematters when the resin is cured, while without substantially injuringproperties of the resulting cured resin. These alkenyl-substitutednadimides are thus considered to exhibit excellent processability, andtheir thermoset products are deemed to have superior heat resistance,mechanical strength, electrical characteristics, and chemical stability.These are thus useful in some degree as a laminating material, moldingmaterial, composite material, coating material, paint, or adhesive.However, these alkenyl-substituted nadimides are insufficient and stillto be improved in their mechanical properties, especially in toughness,and in their adhesion characteristics to substrates.

In the field of heat resistant adhesives, thermosetting polyimides, suchas bismaleimide, polyamino-bismaleimide (KERIMIDE, tradename, Ciba-GeigyAG) , and triazine-modified bismaleimide (BT Resin, tradename,Mitsubishi Gas Chemical Company, Inc.), have been known conventionally.The alkenyl-substituted nadimides are also known to be usable as a heatresistant adhesive. These conventional imides, however, are stillinsufficient in their heat resistance when used as an adhesive for along period of time at a high temperature.

Further, in the field of coating materials a number of thermosettingpolyimides, including said alkenyl-substituted nadimides, are also knownto be usable as coating materials. These conventional thermosettingpolyimide type coating materials are insufficient in their resistance toboiling water, when applied to surfaces exposed to boiling water or hightemperature steam, such as hot water boilers, boiling water tanks, andhot water pipes.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novelalkenyl-substituted bisnadimide, which can produce a thermoset resinwhich does not have the above-mentioned problems, and which exhibitsimproved mechanical strength, especially improved toughness, andexcellent adhesion characteristics to substrates, while maintainingsuperior heat resistance and electrical characteristics inherentlypossessed by conventional alkenyl-substituted nadimide thermoset resins.The present invention further provides a process for manufacturing thisalkenyl-substituted bisnadimide and a process for curing the same.Further, the present invention provides an adhesive which is wellresistive to a high temperature of 250° C. or above for a long period oftime and a coating material which exhibits excellent boiling waterresistance.

We have undertaken extensive studies in order to achieve theabove-mentioned objects and, as a result, have found that a curedproduct of a novel alkenyl-substituted bisnadimide containing a diaminecomponent with a specific structure different from diaminesconventionally used in the preparation of alkenyl-substituted nadimidesexhibits unique characteristics as compared with cured products madefrom conventional alkenyl-substituted nadimides. That is, it hasexcellent mechanical strength, toughness, and adhesion characteristicsto substrates, as well as improved heat resistance. We have furtherfound that this novel alkenyl-substituted bisnadimide can provide anadhesive which exhibits excellent heat resistance at a high temperaturefor a long period of time and can provide a coating material whichexhibits excellent boiling water resistance. These findings have led tothe completion of the present invention.

Accordingly, the gist of the first invention resides in analkenyl-substituted bisnadimide represented by the following formula 1!:##STR3## wherein R¹ and R² individually represent a hydrogen atom or amethyl group, and E is an alkylene.phenylene group or analkylene.phenylene.alkylene group represented by the following formula2!: ##STR4## (wherein a is an integer of 0 or 1, and R³ and R^(3')individually represent a C₁ -C₄ alkylene group or a C₅ -C₈ cycloalkylenegroup)!.

The gist of tile second invention resides in a process for preparingsaid alkenyl-substituted bisnadimide, which comprises reacting analkenyl-substituted bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acidanhydride derivative represented by the following formula 3!: ##STR5##(wherein R¹ and R² individually represent a hydrogen atom or a methylgroup) and a diamine of the following formula 4!:

    H.sub.2 N--E--NH.sub.2                                       4!

wherein E is an alkylene.phenylene group or analkylene.phenylene.alkylene group represented by the following formula2!: ##STR6## (wherein a is an integer of 0 or 1, and R³ and R³ 'individually represent a C₁ -C₄ alkylene group or a C₅ -C₈ cycloalkylenegroup)!.

The gist of the third invention resides in a process for curing saidalkenyl-substituted bisnadimide which comprises heating saidalkenyl-substituted bisnadimide at 80°-400° C. for 0.001-30 hours in theabsence or presence of a curing catalyst.

The gist of the fourth invention resides in an adhesive comprising saidalkenyl-substituted bisnadimide as a curing component.

The gist of the fifth invention resides in a coating material comprisingsaid alkenyl-substituted bisnadimide as a curing component.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an IR spectrum of N,N'-p-xylylene-bis (allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide) (hereinafter referred to BANI-pX)obtained in Example 1;

FIG. 2 is a ¹ H-NMR spectrum of BANI-pX obtained in Example 1;

FIG. 3 is an IR spectrum of N,N'-m-xylylene-bis (allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide) (hereinafter referred to BANI-mX)obtained in Example 2;

FIG. 4 is a ¹ H-NMR spectrum of BANI-mX obtained in Example 2;

FIG. 5 is an IR spectrum ofN,N'-(p-phenylene).ethylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide) (hereinafter referred to BANI-PE)obtained in Example 3;

FIG. 6 is a ¹ H-NMR spectrum of BANI-PE obtained in Example 3;

FIG. 7 is an IR spectrum ofN,N'-(o-phenylene).methylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide) (hereinafter referred to BANI-PM)obtained in Example 4; and

FIG. 8 is a ¹ H-NMR spectrum of BANI-PM obtained in Example 4.

DETAILED DESCRIPTION OF THE INVENTION

The alkenyl-substituted bisnadimide of formula 1! can be synthesized bythe reaction of,

an alkenyl-substituted bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acidanhydride derivative, which is conventionally known to be used for thesynthesis of alkenyl-substituted nadimides and represented by thefollowing formula 3!: ##STR7## wherein R¹ and R² individually representa hydrogen atom or a methyl group (this compound is hereinafter referredto as alkenyl-substituted nadic acid anhydride derivative)!, and

a diamine having a specific structure and represented by the followingformula 4!:

    NH.sub.2 --E--NH.sub.2                                       4!

wherein E is an alkylene.phenylene group or analkylene.phenylene.alkylene group represented by the following formula2!: ##STR8## (wherein a is an integer of 0 or 1, and R³ and R^(3')individually represent a C₁ -C₄ alkylene group or a C₅ -C₈ cycloalkylenegroup)!.

Given as typical examples of alkenyl-substituted nadic acid anhydridederivatives of formula 3! are allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride, methallyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride, allylmethyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride, andmethallylmethyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acidanhydride.

As the E group of the diamines represented by the formula 4!, when the Egroup is phenylene.alkylene structure, for example, phenylene.methylenegroup (wherein phenylene group can be any one of o-, m- andp-configurations, hereinafter the same), phenylene.ethylene group,phenylene.trimethylene group, phenylene.tetramethylene group,phenylene.butylidene group, phenylene.s-butylidene group,phenylene.1-methylethylene group, phenylene.2-methylethylene group,phenylene.1,2-dimethylethylene group, phenylene.1,1-dimethylethylenegroup, phenylene.1,2-cyclopentylene group, phenylene.1,3-cyclopentylenegroup, phenylene.1,4-cyclopentylene group,phenylene.2-methyl-1,4-cyclopentylene group,phenylene.2,3-dimethyl-1,4-cyclopentylene group,phenylene.1,2-cyclohexylene group, phenylene.1,4-cyclohexylene group,phenylene.2methyl-1,3-cyclohexylene group,phenylene.3-methyl-1,4-cyclohexylene group,phenylene.3-ethyl-1,4-cyclohexylene group, phenylene.1,3-cycloheptylenegroup, phenylene.3-methyl-1,4-cycloheptylene group,phenylene.4-methyl-1,3-cycloheptylene group, phenylene.1,3-cyclooctylenegroup and phenylene.1,4cyclooctylene group can be cited. As the E groupof the diamines represented by the formula 4!, when the E group isalkylene.phenylene.alkylene structure, for example, o-, m- andp-xylylene group, methylene.phenylene.ethylene group,methylene.phenylene.trimethylene group,methylene.phenylene.1-methylethylene group,methylene.phenylene.2-methylethylene group,methylene.phenylene.1,2-dimethylethylene group,methylene.phenylene.1,4-cyclopentylene group,ethylene.phenylene.butylidene group, group,butylidene.phenylene.butylidene group,trimethylene.phenylene.s-butylidene group,trimethylene.phenylene.1,3-cyclooctylene group,1,4-cyclopentylene.phenylene.1,4-cyclopentylene group,1,3-cyclooctylene.phenylene.3-ethyl-1,4-cyclohexylene group,1,3-cyclooctylene.phenylene.1,3-cyclooctylene group and1,4-cyclohexylene.phenylene.1,3-cyclooctylene group can be cited. Theaboves are illustrations only, and the E group of formula 4! is notlimited to the above.

Synthesis of the alkenyl-substituted bisnadimide of formula 1! in thepresent invention can be carried out according to conventional processesfor producing alkenyl-substituted nadimides.

Specifically, the alkenyl-substituted bisnadimide of formula 1! of thepresent invention can be prepared almost stoichiometrically by reactingsaid alkenyl-substituted nadic acid anhydride derivative and saiddiamine at 80°-220° C. for 0.5-20 hours in the absence or presence of asolvent.

Alternatively, it can be synthesized by a two step reaction, in whichsaid alkenyl-substituted nadic acid anhydride derivative and saiddiamine are reacted in the presence of a solvent at a relatively lowtemperature first to produce an amic acid which is an intermediate ofthe imide, and then cyclization and imidation are carried out using atertiary amine or, if necessary, a combination of a tertiary amine andnickel acetate, as a catalyst, and acetic anhydride or the like as adehydration agent.

Benzene, toluene, xylene, methylnaphthalene, tetralin, chloroform,trichlene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran,anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone,acetophenone, N,N-dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone, and the like are given as examples of solventsusable in the synthesis.

The alkenyl-substituted bisnadimide of the present invention can bepolymerized and cured by heating at 80°-400° C. for 0.001-30 hours. Itis desirable to use a catalyst to complete the curing reaction at arelatively low temperature in a relatively short period of time.

As curing catalysts for use in the polymerization or curing ofalkenyl-substituted bisnadimide of the present invention, (1) cationiccatalysts, (2) onium salts, (3) organic peroxides, (4) organic compoundsof transition elements, and so on can be cited.

As (1) the cationic catalysts of the above, for example, acids orBrφnsted acids which can liberate protons, and esters thereof or aminecomplexes thereof, such as sulfuric acid, dimethyl sulfate, diethylsulfate, aniline sulfate, sulfuric acide.pyridine complex, phosphoricacid, phosphorous acid, phenylphosphonic acid, phenylphosphinic acid,triethyl phosphate, dimethyl phosphate, diphenyl phosphate, phenylphosphite, methanesulfonic acid, trifluoromethanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonicacid.triphenylamine complex, pyridinium p-toluenesulfonate, pyridiniumm-nitrobenzenesulfonate, α- or β-naphthalenesulfonic acid, methylbenzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate,and N-(2-benzenesulfonylhydroxyethyl)-allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide (ANI-BsE); and for example, halide ofGroup II-V elements of Periodic Table showing Lewis acidity or theircomplexes with bases, or the like, such as boron trichloride, borontrifluoride, boron trifluoride.ether complex, borontrifluoride.piperazine complex, ferric chloride, nickel chloride,stannic tetrachloride, titanium tetrachloride, aluminium chloride,aluminium chloride.ether complex, aluminium chloride.pyridine complex,aluminium bromide, zinc chloride and antimony pentachloride can becited.

As (2) the onium salts, for example, ammonium compounds, such as benzyltriethylammonium chloride, benzyltriethylammonium bromide,benzyltri-n-butylammonium chloride, benzyltri-n-butylammonium bromide,phenyltrimethylammonium bromide, tetra-n-butylammonium chloride,tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate,m-trifluoromethylphenyltrimethylammonium bromide andtetra-n-butylammonium trifluoromethanesulfonate; phosphonium compounds,such as methyltriphenylphosphonium iodide, methyltriphenylphosphoniumbromide, benzyltriphenylphosphonium chloride, tetraphenylphosphoniumbromide and 3-bromopropyltriphenylphosphonium bromide; arsoniumcompounds, such as benzyltriphenylarsonium chloride, tetraphenylarsoniumbromide and tetra-n-butylarsonium chloride; stibonium compounds, such asbenzyltriphenylstibonium chloride and tetraphenylstibonium bromide;oxonium compounds, such as triphenyloxonium chloride andtriphenyloxonium bromide; sulfonium compounds, such astriphenylsulfonium tetrafluoroborate, triphenylsulfoniumhexafluoroarsenate, tri(p-methoxyphenyl)sulfonium hexafluorophosphate,tri-(p-tolyl) sulfonium tetrafluoroborate, dimethylphenacylsulfoniumhexafluorophosphate, dimethylphenacylsulfonium tetrafluoroborate anddiphenylphenacylsulfonium tetrafluoroborate; selenonium compounds, suchas triphenylselenonium tetrafluoroborate, triphenylselenoniumhexafluoroarsenate, triphenylselenonium hexafluoroantimonate and p-(t-butylphenyl)diphenylselenonium hexafluoroarsenate; stannoniumcompounds, such as triphenylstannonium chloride, triphenylstannoniumbromide, tri-n-butylstannonium bromide and benzyldiphenylstannoniumchloride; and iodonium compounds, such as diphenyliodonium chloride,diphenyliodonium bromide, diphenyliodonium perchlorate, diphenyliodoniumtetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodoniumhexafluorophosphate, diphenyliodonium hexafluoroantimonate,(p-methoxyphenyl)phenyliodonium tetrafluoroborate,di(2-nitrophenyl)iodonium hexafluoroarsenate, di(p-tolyl) iodoniumhexafluorophosphate and di(p-chlorophenyl)iodonium hexafluoroarsenatecan be cited.

As (3) the organic peroxides, for example, di-t-butyl peroxide,di-t-amyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetylperoxide, dipropionil peroxide, di-i-butyryl peroxide, benzoyl peroxide,succinic acid peroxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide,cumene hydroperoxide, t-butylperoxy benzoate, t-butylperoxy pivalate,1,1-di-t-butylperoxy cyclohexane, di(t-butylperoxy)isophthalate,t-butylperoxy maleate, t-butylperoxy isopropylcarbonate and2,2-di-t-butylperoxy butane are cited.

As (4) the organic compounds of transition elements, for example, acetylacetonates, organic carboxylic acid salts, metallocenes, alcoholates,chelate compounds and organometallic compounds of transition elementssuch as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Mo, Ru, Rh, La, Ce, Hf, Taand W, and preferably acetyl acetonates of V, Mn, Fe and Ce can becited. Incidentally, joint use of (3) the organic peroxides and (4) theorganic compounds of transition elements is also applicable.

The amount of the curing catalyst used in the reaction can be determinedfrom a wide range with no specific limitations, usually, from a range of0.005-10% by weight, and preferably 0.01-5% by weight, of the amount ofthe alkenyl-substituted bisnadimide.

The alkenyl-substituted bisnadimides of the present invention can beused as a mixture of two or more bisnadimide compounds falling withinthe definition of the present invention, or they may be served for useas an oligomer.

The alkenyl-substituted bisnadimide of the present invention not onlyexhibits the same superior solubility in various solvents asconventional alkenyl-substituted nadimides, but also has more excellentheat resistance, mechanical strength, toughness, and adhesion propertiesto substrate than conventional alkenyl-substituted nadimides. They aredirected to a variety of applications such as a laminating material, acast molding material, a molding material, a coating material, a paint,an adhesive, a filler, and a matrix resin for composite resins usingglass or carbon fibers as a reinforcing material.

Among the above applications, the alkenyl-substituted bisnadimides ofthe present invention are particularly suitable for use as an adhesiveor a coating material. Among the alkenyl-substituted bisnadimides of thepresent invention, particularly preferred compounds for use as anadhesive or a coating material are N,N'-o-xylylene-bis (allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide), N,N'-m-xylylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide), N,N'-p-xylylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide, andN,N'-m-xylylene-bis(methallyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide).

The adhesive comprising the alkenyl-substituted bisnadimide of thepresent invention as a curing component exhibits excellent heatresistance at a high temperature of 250° C. or higher for a long periodof time, and the coating material comprising the alkenyl-substitutedbisnadimide of the present invention as a curing component exhibitsexcellent boiling water resistance.

When the alkenyl-substituted bisnadimide of the present invention isused as an adhesive or a coating material, absence of a curing catalystis rather preferred in view of adhesiveness to substrates or fitness tothe surface to be coated. Of course, a curing catalyst may be presentdepending on the requirements. The use of a solvent is not alwaysessential, because said alkenyl-substituted bisnadimides have a lowsoftening point. When a solvent is used, most common solvents, such asbenzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether,can be acceptable. Further, methylpyrrolidon, dimethylsulfoxide, and thelike, can be also used. These solvents can be used either singly or incombination of two or more. Regarding the concentration ofalkenyl-substituted bisnadimides in the solution when a solvent is used,an extremely dilute solution is used for the purpose of forming thinfilms. On the other hand, a high concentration solution is used foradhesive. Usually, a concentration in the range of 5-70% by weight isapplicable.

There are no limitations as to the manner in which the adhesives or thecoating materials of the present invention are applied. Generalapplication means, such as brushes, applicators, rollers, spatulas andsprays can be used.

In curing the alkenyl-substituted bisnadimide of the present invention,when a solvent is used, it is first removed after the application of theadhesives or the coating materials, then polymerization-curing iscarried out at 80°-400° C., preferably 8°-300° C., for 0.001-10 hours,preferably 0.005-5 hours. In order to complete the curing reaction at arelatively low temperature in a relatively short period of time, the useof the above-mentioned curing catalyst is desirable.

If necessary, adhered products or coated films thus obtained may betreated with heat at 150°-350° C. for 0.5-30 hours.

Carbon black or commonly used pigments such as titanium oxide may beadded to the coating material of the present invention.

The adhesive or the coating material of the present invention can beused for adhering or coating metals, such as steel, aluminium, orcopper; glass, resin, cement, ceramics, and the like. It is especiallyeffective when used as an adhesive requiring heat resistance at a hightemperature of 250° C. or higher for a long period of time, or as acoating material requiring resistance to boiling water for a long periodof time, such as a coating material to be applied to surfaces exposed-toboiling water or high temperature steam, such as hot water boilers,boiling water tanks, and hot water pipes.

When the alkenyl-substituted bisnadimide of the present invention isused for the applications other than adhesives or coating materials, forexample, as a material for molding articles, it is melted together witha curing catalyst, as needed, molded by cast molding, injection molding,or press molding, and cured at 80°-280° C., preferably at 120°-260° C.,for 0.01-8 hours, preferably 0.05-5 hours.

When the alkenyl-substituted bisnadimide of the present invention isused as a matrix resin, various kinds of fillers, such as glass fibers,carbon fibers, metal fibers, ceramic fibers, calcium phosphate, calciumcarbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide,antimony oxide, gypsum, silica, alumina, clay, talc, quarts powders, andcarbon black, in an amount of 10-500 parts by weight, are added to andmixed with 100 parts by weight of the alkenyl-substituted bisnadimide toobtain a composite material.

The present invention is hereinafter illustrated by way of exampleswhich shall not be construed as limiting the present invention.

EXAMPLE 1

To a 500 ml flask replaced with nitrogen 154.3 g (0.756 mol) ofallyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride and 200ml of xylene were charged. To the mixture was added 50 g (0.37 mol) ofp-xylylenediamine over 30 minutes with heating and stirring whilerefluxing xylene. The reaction was continued for 4 hours whileseparating and removing water produced by the reaction by a waterseparator. A trace amount of solid residue was separated by filtrationand the solvent, xylene, was removed by distillation. The content oftime flask was treated with heat at 200° C. under reduced pressure of 1Torr for 1.5 hours while stirring, thus obtaining 183.6 g yield based onamine (hereinafter the same):97%! of the targetN,N'-p-xylylene-bis(allyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboximide),of which the chemical structure is shown by the following formula 5!.This compound is hereinafter abbreviated to BANI-pX. ##STR9##

The IR spectrum and ¹ H-NMR spectrum (60 MHz) of BANI-pX are shown inFIGS. 1 and 2, respectively.

In the IR spectrum, the following absorptions were identified.

Alkene C--H stretching: 3074, 2978 cm⁻¹

Aromatic C--H stretching: 2978 cm⁻¹

Alkane C--H stretching: 2943 cm⁻¹

Imide C═O stretching: 1769, 1699 cm⁻¹

C═C stretching: 1641 cm⁻¹

--CH₂ --N methylene scissors: 1429 cm⁻¹

Imide C--N stretching: 1393 cm⁻¹

In the ¹ H-NMR spectrum, the following peaks were identified.

a-d protons (4H): 7.0-7.3 ppm

e-g protons (8H): 4.7-5.9 ppm

h protons (4H): 4.2-4.7 ppm

i-m protons (12H): 2.2-3.4 ppm

n protons (4H): 0.8-2.0 ppm

The elementary analysis revealed the results of C:75.0 wt. %, H:6.1 wt.%, and N:5.5 wt. % (calculated values, C:75.57 wt. %, H:6.34 wt. %, andN:5.51 wt. %).

The properties of BANI-pX were as follows:

(1) Pale yellow solid with a melting point, measured by a micro meltingpoint apparatus, of about 55° C.

(2) Easily soluble in N,N-dimethylformamide, methyl ethyl ketone,tetrahydrofuran, ethyl acetate, toluene, and the like, and insoluble inhexane and methanol.

EXAMPLE 2

To a 1000 ml flask replaced with nitrogen 257.4 g (1.26 mol) ofallyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride and 300ml of xylene were charged. To the mixture was added 81.4 g (0.60 mol) ofm-xylylenediamine over 1.5 hours with heating and stirring whilerefluxing xylene. The reaction was continued for 3 hours whileseparating and removing water produced by the reaction by a waterseparator, and then the solvent, xylene, was removed by distillation.Thereafter, the content of the flask was treated with heat at 200° C.under reduced pressure of 1 Torr for 1 hour while stirring, thusobtaining 301.8 g (yield: 99%) of the targetN,N'-m-xylylene-bis(allyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboximide),of which the chemical structure is shown by the following formula 6!.This compound is hereinafter abbreviated to BANI-mX. ##STR10##

The IR spectrum and ¹ -NMR spectrum (60 MHz) of BANI-mX are shown inFIGS. 3 and 4, respectively.

In the IR spectrum, the following absorptions were identified.

Alkene C--H stretching: 3075, 2979 cm⁻¹

Aromatic C--H stretching: 2979 cm⁻¹

Alkane C--H stretching: 2943 cm⁻¹

Imide C═O stretching: 1769, 1701 cm⁻¹

C═C stretching: 1641 cm⁻¹

--CH₂ --N methylene scissors: 1428 cm⁻¹

Imide C--N stretching: 1394 cm⁻¹

In the ¹ H-NMR spectrum, the following peaks were identified.

a-d protons (4H): 7.0-7.3 ppm

e-g protons (8H): 4.7-6.0 ppm

h protons (4H): 4.2-4.7 ppm

i-m protons (12H): 2.2-3.4 ppm

n protons (4H): 0.8-1.9 ppm

The elementary analysis revealed the results of C:75.3 wt. %, H:6.4 wt.%, and N:5.4 wt. % (calculated values, C:75.57 wt. %, H:6.34 wt. %, andN:5.51 wt. %).

The properties of BANI-mX were as follows:

(1) Pale yellow solid with a melting point, measured by a micro meltingpoint apparatus, of about 42° C.

(2) Specific Gravity (23° C./23° C.): 1.213

(3) Viscosity: 4.0×10⁴ mPa.s (80° C.) 3.5×10³ mPa.s (100° C.)

(4) Easily soluble in N,N-dimethylformamide, methyl ethyl ketone,tetrahydrofuran, ethyl acetate, toluene, and the like, partly soluble inmethanol and insoluble in hexane.

EXAMPLE 3

To a 300 ml flask replaced with nitrogen 61.7 g (0.302 mol) ofallyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride and 100ml of xylene were charged. To the mixture was added 20 g (0.15 mol) of2-(4-aminophenyl)ethylamine over 30 minutes with heating and stirringwhile refluxing xylene. The reaction was continued for 4 hours whileseparating and removing water produced by the reaction by a waterseparator. A trace amount of solid residue was separated by filtrationand the solvent, xylene, was removed by distillation. Then, the contentof the flask was treated with heat at 200° C. under reduced pressure of1 Torr for 1 hour while stirring, thus obtaining 70.7 g (yield:88%) ofthe target N,N'-(p-phenylene).ethylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide), of which the chemical structure isshown by the following formula 7!. This compound is hereinafterabbreviated to BANI-PE. ##STR11##

The IR spectrum and ¹ H-NMR spectrum (60 MHz) of BANI-PE are shown inFIGS. 5 and 6, respectively.

In the IR spectrum, the following absorptions were identified.

Alkene C--H stretching: 3075, 2977 cm⁻¹

Aromatic C--H stretching: 2977 cm⁻¹

Alkane C--H stretching: 2943 cm⁻¹

Imide C═O stretching: 1772, 1709 cm⁻¹

C═C stretching: 1641 cm⁻¹

--CH₂ --N methylene scissors: 1434 cm⁻¹

Imide C--N stretching: 1394 cm⁻¹

In the ¹ H-NMR spectrum, the following peaks were identified.

a-d protons (4H): 6.8-7.4 ppm

e-g protons (8H): 4.7-6.0 ppm

h-n protons (16H): 2.5-3.9 ppm

o protons (4H): 0.8-1.9 ppm

The elementary analysis revealed the results of C:75.8 wt. %, H:6.2 wt.%, and N:5.4 wt. % (calculated values, C:75.57 wt. %, H:6.34 wt. %, andN:5.51 wt. %).

The properties of BANI-PE were as follows:

(1) Amber solid with a melting point, measured by a micro melting pointapparatus, of about 83° C.

(2) Easily soluble in N,N-dimethylformamide, methyl ethyl ketone,tetrahydrofuran, ethyl acetate, toluene, and the like, and insoluble inhexane and methanol.

EXAMPLE 4

To a 1000 ml flask replaced with nitrogen 172.0 g (0.843 mol) ofallyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboxylic acid anhydride and 200ml of xylene were charged. To the mixture was added 50 g (0.41 mol) of2-aminobenzylamine over 30 minutes with heating and stirring whilerefluxing xylene. The reaction was continued for 4 hours whileseparating and removing water produced by the reaction by a waterseparator. Then, the solvent, xylene, was removed by distillation. Thecontent of the flask was treated with heat at 200° C. under reducedpressure of 1 Torr for 1 hour while stirring, thus obtaining 156.7 g(yield: 77%) of the targetN,N'-(o-phenylene).methylene-bis(allyl-bicyclo2.2.1!hept-5-ene-2,3-dicarboximide), of which the chemical structure isshown by the following formula 8!. This compound is hereinafterabbreviated to BANI-PM. ##STR12##

The IR spectrum and ¹ H-NMR spectrum (60 MHz) of BANI-PM are shown inFIGS. 7 and 8, respectively.

In the IR spectrum, the following absorptions were identified.

Alkene C--H stretching: 3074, 2977 cm⁻¹

Aromatic C--H stretching: 2977 cm⁻¹

Alkane C--H stretching: 2943 cm⁻¹

Imide C═O stretching: 1780, 1709 cm⁻¹

C═C stretching: 1642 cm⁻¹

--CH₂ --N methylene scissors: 1434 cm⁻¹

Imide C--N stretching: 1394 cm⁻¹

In the ¹ H-NMR spectrum, the following peaks were identified.

a-d protons (4H): 6.5-7.4 ppm

e-g protons (8H): 4.5-5.9 ppm

h protons (2H): 4.1-4.5 ppm

i-m protons (12H): 2.3-3.6 ppm

n protons (4H): 0.8-1.9 ppm

The elementary analysis revealed the results of C:75.0 wt. %, H:6.1 wt.%, and N:5.5 wt. % (calculated values, C:75.28 wt. %, H:6.11 wt. %, andN:5.66 wt. %).

The properties of BANI-PM were as follows:

(1) Black solid with a melting point, measured by a micro melting pointapparatus, of about 116° C.

(2) Easily soluble in N,N-dimethylformamide, methyl ethyl ketone,tetrahydrofuran, ethyl acetate, toluene, and the like, partly soluble inmethanol, and insoluble in hexane.

EXAMPLES 5-11

5 g of powder of BANI-mX prepared in Example 2 was blended homogeneouslywith 0.05 g of various kinds of cationic catalysts shown in Table 1. Aportion of each blend was placed on a hot plate exposed to air at atemperature of 200° C. A period of time required for each sample to gel(gelling time) was measured while agitating the mixture at thistemperature. The results are shown in Table 1.

                  TABLE 1    ______________________________________                             Gelling time              Cationic Catalysts                             (min:sec)    ______________________________________    Example 5   Aluminum chloride                                 11:00    Example 6   Ferric chloride  12:00    Example 7   Nickel chloride  15:30    Example 8   Methyl p-toluenesulfonate                                 10:00    Example 9   ANI-BsE          12:00     Example 10 Aniline sulfate  10:30     Example 11 β-naphthalenesulfonic acid                                  8:00    ______________________________________     ANI-BsE:     N(2-benzenesulfonylhydroxyethyl)-allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarb    ximide

EXAMPLES 12-15

5 g of powder of BANI-mX prepared in Example 2 was blended homogeneouslywith 0.05 g of various kinds of cationic catalysts shown in Table 2. Aportion of each blend was placed on a hot plate exposed to air at atemperature of 180° C. A period of time required for each sample to gel(gelling time) was measured while agitating the mixture at thistemperature. The results are shown in Table 2.

                  TABLE 2    ______________________________________                             Gelling time           Cationic Catalysts                             (min:sec)    ______________________________________    Example 12             p-Toluenesulfonic acid                                 20:00    Example 13             Sulfuric acid-pyridine complex                                 20:00    Example 14             Pyridinium p-toluenesulfollate                                 20:00    Example 15             Dimethyl sulfate    12:00    ______________________________________

EXAMPLES 16-18

5 g of powder of BANI-mX prepared in Example 2 was blended homogeneouslywith 0.05 g of various kinds of onium salt catalysts shown in Table 3. Aportion of each blend was placed on a hot plate exposed to air at atemperature of 200° C. A period of time required for each sample to gel(gelling time) was measured while agitating the mixture at thistemperature. The results are shown in Table 3.

                  TABLE 3    ______________________________________                             Gelling time           Onium Salt        (min:sec)    ______________________________________    Example 16             Diphenyliodonium perchlorate                                  4:00    Example 17             Diphenyliodonium    15:00             hexafluorophosphate    Example 18             Diphenyliodonium    17:00             tetrafluoroborate    ______________________________________

EXAMPLES 19-22

5 g of powder of BANI-mX prepared in Example 2 was blended homogeneouslywith 0.05 g of various kinds of the organic compounds of transitionelements shown in Table 4. A portion of each blend was placed on a hotplate exposed to air at a temperature of 200° C. A period of timerequired for each sample to gel (gelling time) was measured whileagitating the mixture at this temperature. The results are shown inTable 4.

                  TABLE 4    ______________________________________           Organic Compound of                             Gelling time           Transition Element                             (min:sec)    ______________________________________    Example 19             Ferric stearate     10:00    Example 20             Manganese (III) acetylacetonate                                 12:00    Example 21             Acetylferrocene     10:30    Example 22             Cerium (III) acetylacetonate                                  8:00    ______________________________________

EXAMPLES 23-24

5 g of powder of BANI-mX prepared in Example 2 was blended homogeneouslywith 0.05 g of two kinds of organic peroxides shown in Table 5. Aportion of each blend was placed on a hot plate exposed to air at atemperature of 200° C. A period of time required for each sample to gel(gelling time) was measured while agitating the mixture at thistemperature. The results are shown in Table 5.

                  TABLE 5    ______________________________________                           Gelling time             Organic Peroxide                           (min:sec)    ______________________________________    Example 23 Dicumyl peroxide                               18:00    Example 24 Cumene hydroperoxide                               20:00    ______________________________________

EXAMPLES 25-27

5 g of powder of BANI-mX prepared in Example 2 were blendedhomogeneously with 0.025 g of dicumyl peroxide and 0.025 g of variouskinds of the organic compounds of transition elemens shown in Table 6. Aportion of each blend was placed on a hot plate exposed to air at atemperature of 200° C. A period of time required for each sample to gel(gelling time) was measured while agitating the mixture at thistemperature. The results are shown in Table 6.

                  TABLE 6    ______________________________________           Organic Compound of                             Gelling time           Transition Element                             (min:sec)    ______________________________________    Example 25             Manganese (III) Acetylacetonate                                  8:30    Example 26             Nickel (II) Acetylacetonate                                 13:00    Example 27             Vanadium (III) Acetylacetonate                                 12:00    ______________________________________

EXAMPLE 28

BANI-pX prepared in Example 1 was melted at 200° C. for 30 minutes undervacuum to deaerate, and charged into a metal mold and heated at 250° C.for 24 hours under atmospheric pressure to obtain a cured product withthe following characteristics.

Glass transition temperature (TMA method, Tg): 308° C.

Coefficient of linear thermal expansion (1/° C.) (JIS-K7197) (Roomtemperature to Tg): 5.19×10⁻⁵

5% weight loss temperature (in nitrogen, TGA method): 444° C.

Flexural strength (JIS-K7203): 10.8 Kg/mm²

Flexural modulus (JIS-K7203): 355 Kg/mm²

EXAMPLE 29

BANI-mX prepared in Example 2 was melted at 200° C. for 30 minutes undervacuum to deaerate, and charged into a metal mold and heated at 260° C.for 20 hours under atmospheric pressure to obtain a cured product withthe following characteristics.

Specific Gravity (JIS-K7112) (23° C./23° C.): 1.222

Glass transition temperature (TMA method, Tg): 308° C.

Coefficient of linear thermal expansion (1/° C.) (Room temperature toTg): 4.83×10⁻⁵

Distortion temperature at load (high load method) (JIS-K7207 A method):311° C.

5% weight loss temperature (in nitrogen, TGA method): 437° C.

Flexural strength: 14.3 Kg/mm²

Flexural modulus: 391 Kg/mm²

Tensile strength (JIS-K7113): 7.7 Kg/mm²

Tensile modulus (JIS-K7113): 370 Kg/mm²

Compressive strength (JIS-K7208): 18.2 Kg/mm²

Izod impact value (JIS-K7110): 1.8 kj/m²

Rockwell hardness (JIS-K7202): 127 HRM

Volume resistivity (JIS-K6911) (500 V D.C 1 min): 9.41×10¹ 6 Ω·cm

Surface resistivity (JIS-K6911) (500 V D.C 1 min): 2.81×10¹ 6 Ω

Dielectric constant (ε) (JIS-K6911) (1 MHz): 3.09

Dielectric loss (tanδ) (JIS-K6911) (1 MHz): 1.11×10⁻²

EXAMPLE 30

BANI-mX prepared in Example 2 was melted at 170° C. and 1 wt. % ofdiphenyliodonium hexafluorophosphate was added thereto and dissolvedtherein. Thereafter, time molten material was deaerated for 2 minutesand charged into a metal mold and heated at 200° C. for 10 hours underatmospheric pressure to obtain a cured product with the followingcharacteristics.

Glass transition temperature (TMA method, Tg): 221° C.

Flexural strength: 16.0 Kg/mm²

Flexural modulus: 380 Kg/mm²

EXAMPLE 31

A curing test was conducted in the same manner as in Example 30 exceptthat 1 wt. % of pyridinium p-toluenesulfonate was used instead of 1 wt.% of diphenyliodonium hexafluorophosphate used in Example 30. A curedproduct having the following characteristics was obtained.

Glass transition temperature (TMA method, Tg): 216° C.

Flexural strength: 13.5 Kg/mm²

Flexural modulus: 403 Kg/mm²

EXAMPLE 32

BANI-PE prepared in Example 3 was melted at 200° C. for 30 minutes undervacuum to deaerate, and charged into a metal mold and heated at 250° C.for 24 hours under atmospheric pressure to obtain a cured product withthe following characteristics.

Glass transition temperature (TMA method, Tg): 306° C.

Coefficient of linear thermal expansion (1/° C. ) (Room temperature toTg): 5.23×10⁻⁵

5% weight loss temperature (in nitrogen, TGA method): 444° C.

Flexural strength: 11.1 Kg/mm²

Flexural modulus: 340 Kg/mm²

EXAMPLE 33

BANI-PM prepared in Example 4 was melted at 200° C. for 30 minutes undervacuum to deaerate, and charged into a metal mold and heated at 250° C.,for 24 hours under atmospheric pressure. A cured product having 5%weight loss temperature (in nitrogen, TGA method) of 403° C. wasobtained.

Comparative Example 1

Bis 4-(allyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboximide)phenyl!methane(hereinafter referred to BANI-M) was prepared according to the processdescribed in U.S. Pat. No. 4,515,962. BANI-M thus obtained was cured inthe same manner as in Example 29 to obtain a cured product with thefollowing characteristics.

Specific Gravity (23° C./23° C.): 1.219

Glass transition temperature (TMA method, Tg): 336° C.

Coefficient of linear thermal expansion (1/° C.) (Room temperature toTg): 5.15×10⁻⁵

Distortion temperature at load (high load method): 348° C.

5% weight loss temperature (in nitrogen, TGA method): 445° C.

Flexural strength: 13.8 Kg/mm²

Flexural modulus: 336 Kg/mm²

Tensile strength: 4.0 Kg/mm²

Tensile modulus: 296 Kg/mm²

Compressive strength: 19.4 Kg/mm²

Izod impact value: 1.1 kj/m²

Rockwell hardness: 128 HRM

Volume resistivity (500 V D.C 1 min): 1.74×10¹ 7 Ω·cm

Surface resistivity (500V D.C 1 min): 1.87×10¹ 7 Ω

Dielectric constant (ε) (1 MHz): 3.18

Dielectric loss (tanδ) (1 MHz): 1.20×10⁻²

Comparative Example 2

N,N'-hexamethylene-bis(allyl-bicyclo 2.2.1!hept-5-ene-2,3-dicarboximide)(hereinafter referred to BANI-H) was prepared according to the processdescribed in U.S. Pat. No. 4,515,962. BANI-H thus obtained was cured inthe same manner as in Example 29 to obtain a cured product with thefollowing characteristics.

Specific Gravity (23° C./23° C.): 1.196

Glass transition temperature (TMA method, Tg): 309° C.

Coefficient of linear thermal expansion (1/° C.) (Room temperature toTg): 6.73×10⁻⁵

Distortion temperature at load (high load method): 307° C.

5% weight loss temperature (in nitrogen, TGA method): 438° C.

Flexural strength: 11.6 Kg/mm²

Flexural modulus: 201 Kg/mm²

Tensile strength: 5.5 Kg/mm²

Tensile modulus: 244 Kg/mm²

Compressive strength: 14.2 Kg/mm²

Izod impact value: 1.5 kj/m²

Rockwell hardness: 123 HRM

Volume resistivity (500 V D.C 1 min): 3.22×10¹ 7 Ω·cm

Surface resistivity (500 V D.C 1 min): >1.00×10¹ 7 Ω

Dielectric constant (ε) (1 MHz): 2.88

Dielectric loss (tanδ) (1 MHz): 1.04×10⁻²

EXAMPLES 34-37 Comparative Examples 3-6

Solutions of alkenyl-substituted bisnadimides (30 wt. %) in xylene shownin Table 7 were applied to mild steel plate by spraying and baked at200° C. for 20 minutes in air. All produced a coated film with athickness of 10-15 μm exhibiting superior adhesion properties andsolvent resistance.

These test specimens were placed in a thermostat at 300° C. for aprescribed period of time and their adhesion properties were examined.The results are shown in Table 7.

                  TABLE 7    ______________________________________                   Holding time in the thermostat            Sample   16 hours    100 hours    ______________________________________    Example 34              BANI-PM    ◯                                     ◯    Example 35              BANI-PE    ◯                                     ◯    Example 36              BANI-pX    ◯                                     ◯    Example 37              BANI-mX    ◯                                     ◯    C. Example 3              BANI-H     X           X    C. Example 4              BANI-M     ◯                                     X    C. Example 5              BANI-PD    ◯                                     X    C. Example 6              BANI-TD    X           X    ______________________________________     C. Example: Comparative Example     Test procedure for determining adhesion property: JISK5400 cheker test     ◯: 100% retained; Δ: 99-95% retained, i.e., 1-5%     damaged; X: less than 95% retained, i.e., more than 5% damaged.     BANIPM: N,N(o-phenylene).methylene     bis(allylbicyclo 2.2.1!hept5-ene-2,3-dicarboximide)     BANIPE: N,N(p-phenylene).ethylene     bis(allylbicyclo 2.2.1!hept5-ene-2,3-dicarboximide)     BANIpX: N,Np-xylylene-bis(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarboximide     BANImX: N,Nm-xylylene-bis(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarboximide     BANIH:     N,Nhexamethylene-bis(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarboximide)     BANIM:     Bis 4(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarboximide)phenyl!methane     BANIPD:     N,Nm-phenylene-bis(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarboximide)     BANITD:     N,N(1-methyl-2,4-phenylene)-bis(allyl-bicyclo 2.2.1!hept5-ene-2,3-dicarbo    imide)

EXAMPLES 38-41 Comparative Examples 7-10

Solutions of alkenyl-substituted bisnadimides (30 wt. %) in xylene shownin Table 7 were applied to aluminum plate by spraying and baked at 200°C. for 20 minutes in air. All produced a coated film with a thickness of10-15 μm exhibiting superior adhesion properties and solvent resistance.

These test specimens were placed in a thermostat at 300° C. for aprescribed period of time and their adhesion properties were examined.The results are shown in Table 8.

                  TABLE 8    ______________________________________                   Holding time in the thermostat            Sample   16 hours    100 hours    ______________________________________    Example 38              BANI-PM    ◯                                     ◯    Example 39              BANI-PE    ◯                                     ◯    Example 40              BANI-pX    ◯                                     ◯    Example 41              BANI-mX    ◯                                     ◯    C. Example 7              BANI-H     X           X    C. Example 8              BANI-M     ◯                                     X    C. Example 9              BANI-PD    X           X    C. Example 10              BANI-TD    X           X    ______________________________________     Test procedure for determining adhesion property and abbreviations are th     same as shown relative to Table 7.

EXAMPLE 42

A 50 wt. % methyl ethyl ketone solution of BANI-mX prepared in Example 2was applied to two mild steel plates (10×2.5×0.2 cm). After drying at160° C. for 20 minutes, the two plates were put together, with thecoated surfaces vis-a-vis facing, fixed with a clip, and the clippedplates were cured by heating at 250° C. for 3 hours. The test specimensthus obtained were left in an air-circulation type thermostat at 250° C.for a prescribed period of time, i.e., 0 day, 5 days, 10 days, 20 daysor 30 days, and a tensile-shearing test (JIS-K6850) was carried out atroom temperature and at 250° C. The results are shown in Table 9.

Comparative Example 11

A similar test was carried out in the same manner as in Example 42except that BANI-H was used instead of BANI-mX used in Example 42. Thespecimens thus obtained were subjected to tensile-shearing test in thesame manner as in Example 42. The results are shown in Table 9.

Comparative Example 12

A similar test was carried out in the same manner as in Example 42except that BANI-M was used instead of BANI-mX used in Example 42. Thespecimens thus obtained were subjected to tensile-shearing test in thesame manner as in Example 42. The results are shown in Table 9.

Comparative Example 13

A similar test was carried out in the same manner as in Example 42except that commercially available thermosetting polyimide (BT resin,tradename; Mitsubishi Gas Chemical Company, Inc.) was used instead ofBANI-mX used in Example 42. The specimens thus obtained were subjectedto tensile-shearing test in the same manner as in Example 42. Theresults are shown in Table 9.

                  TABLE 9    ______________________________________    Adhesion strength obtained by tensile-    shearing test (Kg/cm.sup.2)               Ex. 42 C. Ex. 11                               C. Ex. 12                                        C. Ex. 13    ______________________________________    Initial value    At room temperature                 202      186      166    240    At 250° C.                 157      108      97     150    After 5 days    At room temperature                 185      176      102    219    At 250° C.                 105       85      67     135    After 10 days    At room temperature                 164      160      76      68    At 250° C.                  95       87      27      22    After 20 days    At room temperature                 167      159      41      20    At 250° C.                 103       79      12     --    After 30 days    At room temperature                 130      125      41     --    At 250° C.                 100       60      10     --    ______________________________________     Ex.: Example;     C. Ex.: Comparative Example;     --: Not measured

EXAMPLE 43

A solution prepared by dissolving 30 g of BANI-mX and 5 g of carbonblack in 70 g of toluene and stirring the mixture at room temperaturefor 30 minutes was applied to a mild steel plate (15×7×0.1 cm). Afterdrying at 130° for 60 minutes, BANI-mX was cured at 180° C. for 20minutes to obtain a boiling water resistant test specimen with a coatedfilm thickness of 15 μm. The test specimen was dipped in a boiling waterat 100° C. in a thermostat for 100 hours, whereupon it was taken outfrom the thermostat and allowed to cool to room temperature. Acellophane tape was evenly attached to the coated surface and peeled offafter 10 minutes, and found that there are no release of the coatedfilm.

Comparative Example 14

The same test as in Example 43 was carried out, except that BANI-M wasused instead of BANI-mX. A cellophane tape was evenly attached to thecoated surface and peeled off after 10 minutes, and found that over 60%area of the coated film was peeled off together with the cellophane tapeattached.

Comparative Example 15

The same test as in Example 43 was carried out, except that BANI-H wasused instead of BANI-mX. A portion of the coated film was released inthe thermostat. Thus, no cellophane tape attachment test could becarried out.

We claim:
 1. An alkenyl-substituted bisnadimide represented by thefollowing formula (1): ##STR13## wherein R¹ and R² individuallyrepresent a hydrogen atom or a methyl group, and E is analkylene.phenylene group or an alkylene.phenylene.alkylene grouprepresented by the following formula (2): ##STR14## (wherein a is aninteger of 0 or 1, and R³ and R^(3') individually represent a C₁ -C₄alkylene group or a C₅ -C₈ cycloalkylene group).
 2. Thealkenyl-substituted bisnadimide according to claim 1, wherein R¹ and R²in formula (1) are a hydrogen atom, respectively.
 3. Thealkenyl-substituted bisnadimide according to claim 1, wherein E informula (1) is selected from the group consisting of aphenylene.methylene group, a phenylene.ethylene group and a xylylenegroup.
 4. The alkenyl-substituted bisnadimide according to claim 1,wherein R¹ and R² in formula (1) are a hydrogen atom, respectively, andE in formula (1) is selected from the group consisting of aphenylene.methylene group, a phenylene.ethylene group and a xylylenegroup.
 5. The alkenyl-substituted bisnadimide according to claim 4,wherein E is a xylylene group.